CN102175503A - Method and apparatus for removing selenium oxide, and method and apparatus for measuring mercury by using the same - Google Patents
Method and apparatus for removing selenium oxide, and method and apparatus for measuring mercury by using the same Download PDFInfo
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- CN102175503A CN102175503A CN2011100277881A CN201110027788A CN102175503A CN 102175503 A CN102175503 A CN 102175503A CN 2011100277881 A CN2011100277881 A CN 2011100277881A CN 201110027788 A CN201110027788 A CN 201110027788A CN 102175503 A CN102175503 A CN 102175503A
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- selenium oxide
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 81
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000001816 cooling Methods 0.000 claims abstract description 116
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000003245 coal Substances 0.000 claims abstract description 53
- 238000002485 combustion reaction Methods 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000000498 cooling water Substances 0.000 claims abstract description 7
- 238000012360 testing method Methods 0.000 claims description 219
- 239000007789 gas Substances 0.000 claims description 159
- 238000012545 processing Methods 0.000 claims description 49
- 238000005201 scrubbing Methods 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 39
- 238000004458 analytical method Methods 0.000 claims description 37
- 230000008676 import Effects 0.000 claims description 36
- 230000001603 reducing effect Effects 0.000 claims description 35
- 230000002829 reductive effect Effects 0.000 claims description 29
- 238000003556 assay Methods 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 18
- 150000001553 barium compounds Chemical class 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 8
- 230000001351 cycling effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 230000007774 longterm Effects 0.000 abstract description 12
- 229910018162 SeO2 Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 21
- 239000011669 selenium Substances 0.000 description 21
- 229910000645 Hg alloy Inorganic materials 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 230000008033 biological extinction Effects 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000010790 dilution Methods 0.000 description 8
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 7
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 239000003957 anion exchange resin Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 229960002523 mercuric chloride Drugs 0.000 description 6
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- BGOFCVIGEYGEOF-UJPOAAIJSA-N helicin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1C=O BGOFCVIGEYGEOF-UJPOAAIJSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229940100892 mercury compound Drugs 0.000 description 4
- 150000002731 mercury compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 210000002706 plastid Anatomy 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940082569 selenite Drugs 0.000 description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KYKQHSMYWLWROM-UHFFFAOYSA-N ac1l4yjn Chemical compound [Hg].[Hg] KYKQHSMYWLWROM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ARSLNKYOPNUFFY-UHFFFAOYSA-L barium sulfite Chemical compound [Ba+2].[O-]S([O-])=O ARSLNKYOPNUFFY-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910001561 spheroidite Inorganic materials 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0045—Hg
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/408—Alkaline earth metal or magnesium compounds of barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
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- Food Science & Technology (AREA)
- Biochemistry (AREA)
- Combustion & Propulsion (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The object of the invention is to provides a method and an apparatus for removing SeO2 in a long term by using a simple means. There is provided a method and apparatus for removing selenium oxide in a sample as well as a method and apparatus for measuring mercury in coal combustion exhaust gas by using the same. The apparatus for removing selenium oxide in a sample, comprising: (1) a heating introduction path for heating a sample, (2) a primary cooling unit having a flow path through which the heated sample flows countercurrently to cooling water, whereby the heated sample is mixed with, and cooled by, cooling water, (3) a secondary cooling unit having a spiral flow path for cooling the mixed gas and having a space for gas/liquid separation at the end of the spiral flow path, (4) a regenerator for introducing condensed water from the secondary cooling unit, and (5) a condensed water-cooling path for connecting the regenerator to the primary cooling unit.
Description
The application is based on dividing an application of following Chinese patent application:
The original bill applying date: on February 2nd, 2008
Original bill application number: 200810005096.5
Original bill application title: mercury assay method and determinator that selenium oxide is removed method and removed device and use it
Mercury assay method and determinator that selenium oxide is removed method and removed device and use it
Technical field
The present invention is about the method for removing the selenium oxide in the test portion and remove device and used mercury assay method and determinator in its coal combustion emission gases, about having reduced metal oxide and the sulphuric dioxide (SO that gasifies in the coal combustion emission gases that stems from combustion of fossil fuel facility, particularly coal combustion facility
2) wait the full mercury assay method and the determinator of the influence that hinders the coexistence composition that full mercury measures.
Background technology
All the time, the use of the employed JIS of the being K of the determinator of the all-metal mercury in the combustion gas 0222 regulation serial testing or use the fixedly generation source mercury determinator of the dilution metering of golden mercury alloy.Here, used the dilution metering of golden mercury alloy to refer to, after at high temperature making mercury compound be reduced to mercury metal the test portion gas, dilution, mercury is caught as golden mercury alloy, behind the certain hour, at high temperature make mercury alloy mercury gasify again, measure the cold atomic absorption spectrometry (for example with reference to non-patent gazette 1) of mercury metal with ultraviolet light absorption method.
But, be accompanied by the expansion of present purposes, for example, during mercury in measuring the emission gases of incinerator etc., in the above-mentioned classic method, owing to have oxides of nitrogen (NO in the emission gases
x) and sulphuric dioxide (SO
2) or hydrogen chloride (HCl) etc. and being affected, therefore be difficult to obtain possessing the measured value of abundant precision.At present, improve the assay method that this assay method maybe will be looked for novelty, following various motion is arranged at requiring.
Concrete, as shown in figure 12, continuous analytic approach as gas shape mercury contained in the emission gases such as mud and offal treatment, there is motion to propose, after as required mercurous gas being heated (about 230 ℃), use by the metal (metallic tin that directly heats (about 200 ℃) with gaseous state, metallic zinc etc.) 21 pairs of the solid reduction catalyzer that is constituted contain mercury gas to be handled, to contain the compound mercury (chloride in the mercury gas, oxide etc.) be reduced to mercury metal, carry out method for measuring (for example with reference to patent gazette 1) by no flame (flameless) atomic absorption spectroscopy device 22.
In addition, as Figure 13 (A) and (B), the device 31 that contains the mercury in the gas of mercuric chloride as analysis, fill reductive agent 34 in reduction reactor 35, reductive agent 34 is formed with the tunicle 33 of stannous chloride by particle 32 surfaces of tin and constitutes, by reduction apparatus 36, make above-mentioned gas pass through reduction reactor 35, at this moment, by reductive agent 34, with the Hg in the mercuric chloride
2+Be reduced to Hg
0, with 37 couples of Hg that are reduced of analyzer (no flame atom absorption spectrophotography device)
0Analyze.Like this, even under the lower situation of hydrogen chloride in gas gas concentration, also can correctly carry out mercury analysis (for example with reference to patent gazette 2).
[non-patent literature 1] JIS K 0222-1997
[patent documentation 1] special fair 1-54655 communique
[patent documentation 2] spy opens the 2001-33434 communique
Summary of the invention
But, use above-mentioned assay method or determinator, when the coal combustion emission gases is measured, because the metal oxide (selenium oxide (SeO in the emission gases that is coexisted
2) wait other metal oxides, be gas) or gas componant SO
2, NO
2And the interference effect of moisture, can't carry out correct mensuration.
That is, in atomic absorption spectroscopy,, therefore can't ignore the high concentration SO of the several 1000ppm levels that coexist in the coal combustion emission gases because utilization is the light absorption of ultraviolet region
2And NO
2Existence and the interference effect that is subjected to.
In addition, for metal oxide, the checking by the inventor as can be known, in the reduction treatment process of mercury compound, carry out the reduction reaction with mercury compound simultaneously, easily make mercury and mercury alloy, the mensuration loss of mercury increases, and can't measure the mercury composition, or the mensuration precision significantly descends.Particularly in the coal combustion emission gases, owing to exist more relatively lead (Pb) and selenium (Se) etc. easily to form the oxide of the metal of mercury and mercury alloy, therefore can't ignore its influence, above-mentioned traditional method is difficult to avoid this problem.
Particularly in long-term use, remove SeO
2Be must be obligato, but in fact its method does not obtain establishing as yet, removing efficient for it has strict requirement.That is, when remover not being set, the pipe arrangement inside surface under the reducing condition of mercury, as one man can generate umbrinaceous element S e, concentrate to result from the slower place of gas flow rate, the result of mercury determinator checking is, the Hg measured value descends gradually, reduces to about about 1 week and makes an appointment with half.When measuring concentration is 10 μ g/m
3Extremely low concentration near mensuration in, this tendency is bigger.That is, even if the SeO of trace
2, mercury alloy also can be grown gradually, the possibility that its influence can occur enlarge, and this needs bear in the test portion disposal system of long-term use, need not be to be 90% but 95% or the higher SeO that removes that removes efficient
2Method.
In addition, for the golden mercury alloy dilution metering of JIS K 02222 defined, have dilution error big, can only batch measure, the problems such as performance degradation of high temperature reduction catalyzer.Concrete, have: (a) corrosion of adhering to, contact the material of gas of high temperature deterioration, the dust of catalyzer material causes the reoxidizing of easy generation mercury, (b) because the SO that coexists
2Oxidation atomizing and produce attached component, thereby the problem of maintenance property difference such as acid elution tower etc. must be set.
In addition, although there is as above demand, be that the CONTINUOUS VISCOSITY MEASURING of the mercury that carries out of the extraction sampling mode beyond the dilution method of object does not obtain substantial exploitation as yet with the coal combustion emission gases.
Therefore, the present invention is corresponding this demand, and purpose provides: be used for preventing generting element Se in mercury mensuration of coal combustion emission gases etc., method and apparatus simple to operate, as can to remove element S e steadily in the long term, wherein, element S e is by the SeO that is present in the emission gases
2And produce, can counteract in the mercury mensuration in the coal combustion emission gases etc., in addition, but provide used this remove method and remove device, mercury assay method and determinator in the coal combustion emission gases of the influence of the composition that do not coexisted, high precision and long-time stability high METHOD FOR CONTINUOUS DETERMINATION.
The inventor is by wholwe-hearted research, found that, remove method and remove device, and used mercury assay method and determinator in its coal combustion emission gases by the selenium oxide in the test portion as follows, can reach above-mentioned purpose, thereby finish the present invention.
The present invention is that the selenium oxide in the test portion is removed method, it is characterized in that:
(1) test portion is heated,
(2) carry out the cooling processing that this test portion with the condition of high temperature mixes, cools off with chilled water,
When (3) carrying out this mixed gas carried out gas-liquid separation and handle, the secondary cooling processing of cooling off again,
(4) to carrying out Regeneration Treatment by the condensate water that reclaims by this secondary cooling processing,
(5) the chilled water cycling and reutilization of using as an above-mentioned cooling processing.
In addition, the present invention is that the selenium oxide in the test portion is removed device, and it is characterized in that possessing has:
(1) the heat heating of test portion imports the road,
(2) have heating test portion stream and cooling water flow form convection current stream, will heat test portion and the cooling end of chilled water mixing to cool off,
When (3) having the spiral fashion stream of the above-mentioned mixed gas of cooling, have the secondary cooling end in the space of carrying out gas-liquid separation in the terminal of this spiral fashion stream,
(4) import regenerator from the condensate water of this secondary cooling end,
(5) chilled water that connects this regenerator and a cooling end is supplied with the road.
As mentioned above, can know, during the mercury in emission gases is measured, the SeO that exists in the test portion
2When reduction reaction, easily make mercury and mercury alloy, this is to measure one of remarkable great reason that descends of precision.That is, as shown in the formula 1, SeO
2Have in coexistence under the situation of moisture and generate selenous acid (H
2SeO
3), as shown in the formula 2, with the SO of coexistence
2Or NO
2Reaction generting element Se.Particularly, know in inventor's checking that under the coexistence of moisture, pyroreaction speed is fast more.In addition, as shown in the formula 3, element S e can generate mercury (Hg) and mercury alloy.At this moment, because element S e adheres to and solidifies on stream, quicken to generate the mercury mercury alloy, precision is measured in influence more.
SeO
2+ H
2O → H
2SeO
3(formula 1)
H
2SeO
3+ SO
2→ Se+H
2SO
4(formula 2)
Hg+Se → HgSe ... (formula 3)
In traditional method, be difficult under the situation of the mensuration that does not influence mercury, remove SeO
2, among the present invention, verified that selectivity removes SeO
2Method, by getting rid of this kind influence, can guarantee the mensuration precision that classic method is difficult to realize.
That is, by containing SeO
2Test portion from heating-up temperature 100-200 ℃ state quench cooled to environmental gas temperature (being generally about 0-30 ℃), quicken the dissolving in the condensate water of the moisture in resulting from test portion, can promote the reaction of following formula 1.But, pass through SO
2Or NO
2Dissolving, this moment, the existence of drops condensate water became the reaction induced of formula 2, by supplying with chilled water, produced the effect of cleaning stream, can suppress the reaction of formula 2.In addition, supply with chilled water and promoting H
2SeO
3When being dissolved in chilled water, also can obtain lysed H
2SeO
3And SO
2Dilution effect.And then, by the low temperatureization of chilled water, can further reduce the reaction of formula 3.The present invention finds according to checking, by having stream that heating test portion stream and cooling water flow are convection current, mixing test portion and chilled water and quench cooled, can improve the actual effect of this kind technique effect.
In addition, among the present invention, handle, can make to get rid of and remove SeO when generating mercury alloy by mixed gas is further carried out gas-liquid separation while cooling off in spiral helicine stream
2Test portion gas.That is,, the drop and the spittle in stream, occur, handle Yi Bian in the space that is arranged at spiral helicine stream terminal, effectively carry out gas-liquid separation on one side can prevent to follow the generation of the conveying of mixed gas and condensate water by the narrow flow path of cooling spiral shape.
In addition, the chilled water of usefulness is not once cooled off in continuous supply from the outside, and with the resulting condensate water of gas-liquid separation as the chilled water that is supplied in a cooling end, from economize on resources, energy-conservation or alleviate the viewpoint of draining burden, also comparatively desirable.That is contained SeO in the test portion,
2Deng water-soluble substances is trace, by condensate water being flow through regenerating unit such as ion exchange resin, can relatively easily remove selenous acid.In addition, when being test portion with the coal combustion emission gases, contain a large amount of moisture in the test portion, need not to replenish chilled water, this recycling is comparatively to be suitable for for long-term use.
By above structure, can provide simple to operate, remove SeO in the test portion steadily in the long term
2Method and apparatus.
In addition, can use cooling processing portion to replace the combination of an above-mentioned cooling end and secondary cooling end, this cooling processing portion possesses and has: the space of carrying out gas-liquid separation, (d) that (a) is positioned at the admission port of the above-mentioned chilled water of spiral helicine stream upstream, supply port that (b) is positioned at the above-mentioned test portion in this downstream, admission port, terminal that (c) is arranged on above-mentioned spiral helicine stream discharges stream by the condensate water of this space branch and the cooling device in discharge stream, (e) above-mentioned each stream of cooling and the space of the gas that disposes.
As mentioned above, the SeO in the eliminating test portion
2One of the emphasis of the present invention of influence be, under the temperature conditions that does not produce water droplet, contact with the chilled water gas-liquid, in general cooling processing and the combination of secondary cooling processing are comparatively desirable.But less as the thermal capacity of the test portion of gas, on the other hand, the thermal capacity of chilled water is big and can be cooled near 0 ℃, therefore under the less situation of the treatment capacity of test portion, can carry out cooling processing and secondary cooling processing simultaneously.The present invention is except this kind function, also by supplying with chilled water from upstream, possess the better heat exchanger effectiveness of spiral fashion stream and being ejected to the space that has enlarged from this stream of thin tube-like, prevent that when gas-liquid separation the water droplet and the spittle from sneaking into the gas that disposed and discharging stream, realized more miniaturization and cooling processing efficiently.
The present invention is that the selenium oxide in the above-mentioned test portion is removed method, it is characterized in that: with test portion under heating condition by being filled with the scrubbing tower of barium compound or ferriferous oxide or their potpourri, selectivity is removed selenium oxide.
The present invention is that the selenium oxide in the above-mentioned test portion is removed device, it is characterized in that: possess the heating that the test portion of heating is arranged and import the road; Be filled with the scrubbing tower of barium compound or ferriferous oxide or their potpourri; This scrubbing tower is maintained the heating arrangement of uniform temperature, selenium oxide is carried out selectivity remove processing.
During as above by the cold water process test portion, contain in the test portion under the situation of water miscible mensuration composition, dissolving can cause error at measurment.For example, with coal combustion emission gases etc. during as test portion, mercuric chloride (Hg
2+) a part be dissolved in chilled water, therefore exist to be reduced to mercury metal (Hg earlier
0) after the restriction that test portion is handled such as handle again, must remove selenium oxide in selectivity under the drying condition.At this moment, be difficult under the condition that does not influence mercury mensuration, remove SeO
2, there is no effective method in the past.The present invention is by to having used various metallic compounds to come selectivity to remove SeO
2Method verify that the back finds, barium compound or ferriferous oxide be by the reaction shown in the following formula 4 and 5, can optionally with SeO
2When reacting, can set the condition that is subjected to react or adsorb the influence that produces hardly with mercury.
SeO
2+ BaCO
3→ BaSeO
3+ CO
2(formula 4)
XSeO
2+ yFeO → FexSey+ (x+y/2) O
2(formula 5)
Therefore, even water miscible mensuration composition and SeO
2The test portion of coexistence by above-claimed cpd is used as scrubbing tower, can carry out selectivity to test portion and remove SeO under drying condition
2Processing, can guarantee the mensuration precision of this mensuration composition.
The present invention is that the selenium oxide in the above-mentioned test portion is removed method, it is characterized in that: the selectivity of an above-mentioned cooling processing and the combination of secondary cooling processing, above-mentioned selenium oxide is removed processing and is carried out with serial or parallel connection.
In addition, the present invention is that the selenium oxide in the above-mentioned test portion is removed device, it is characterized in that: an above-mentioned refrigeratory and recoler combination or above-mentioned cooling processing portion and above-mentioned scrubbing tower are with the serial or parallel connection setting.
For the SeO in the test portion
2Remove, checking found that, as the processing (hereinafter referred to as " wet process ") under the wet condition of an above-mentioned cooling processing and the combination of secondary cooling processing with by these 2 effective methods of processing (hereinafter referred to as " dry-cure ") under the drying condition of scrubbing tower.For each method, as described later, can guarantee the efficient of removing more than 95%, but also certain maintaining must be arranged on the other hand in distinctive advantage separately.That is, although wet process can still can keep and remove efficient through long-time use,, compare with dry-cure that to remove efficient lower.In addition, according to the coexistence composition in the test portion, the test portion disposal route can limit to some extent.Although dry-cure can guarantee high selectivity and remove efficient,, can be consumed because of reaction as the barium compound or the ferriferous oxide of scrubbing tower, therefore have term of life.The present invention is by two kinds of method serial or parallel connections are made up, in the hope of use that they are complemented one another.
Concrete, in long-term the use, even there is the composition of not removing 1% below, its influence also may enlarge gradually, replenishes by two kinds of method tandem compounds and uses, and can provide to bear this kind test portion disposal system of use for a long time.That is, under the situation of the downstream of wet process configuration dry-cure, can be with micro-SeO residual in the test portion after the wet process
2Be reduced to the ultramicron rank by dry-cure.In addition, even coal combustion boiler etc., owing to when boiler is brought into use, contain a large amount of mercury or SeO in the test portion
2Deng, when running well, they can become trace.Under the corresponding situation, by wet process configuration in parallel, carry out wet process, carry out dry-cure the latter at the former with dry-cure, can replenish both load, lighten the load.
The present invention has been to use the selenium oxide in the above-mentioned test portion to remove method or has removed mercury assay method in the coal combustion emission gases of device, it is characterized in that: with the coal combustion emission gases is the determination object test portion, use and above-mentionedly remove method or remove device, measure by the mercury analysis meter to gathering after the above-mentioned test portion of test portion collection portion is handled.
In addition, the present invention has been to use the selenium oxide in the above-mentioned test portion to remove method or has removed mercury determinator in the coal combustion emission gases of device, it is characterized in that: with the coal combustion emission gases is the determination object test portion, and possessing has: gather above-mentioned test portion test portion collection portion, import road, above-mentioned device, the mercury analysis meter removed from heating of this test portion collection portion and the test portion that imports above-mentioned test portion.
When measuring the mercury in the emission gases, by with mercury compound reduction, as atom shape mercury with Their Determination by Spectrophotometry, can realize the mensuration of high sensitivity, on the other hand, during mercury in measuring the coal combustion emission gases, the several problems that do not have before must overcoming.Particularly, be present in SeO in the emission gases
2Owing to when reduction reaction, easily make mercury and mercury alloy, be to cause to measure one of great reason that precision significantly descends, the present invention is by using selenium oxide in the above-mentioned test portion and remove method or removing device and get rid of this influence, the method that can the guarantee the past mensuration precision that is beyond one's reach.Therefore, but mercury assay method and determinator in the coal combustion emission gases of influence, high precision and long-time stability high METHOD FOR CONTINUOUS DETERMINATION of the composition that is not subjected to coexist can be provided.
The present invention is the mercury assay method in the above-mentioned coal combustion emission gases, it is characterized in that: use above-mentioned remove method or remove device above-mentioned test portion is handled after, utilize ultraviolet light-absorbing type analysis meter, the catalyzer of the inorganic by having reducing power is made reduced gas that the mercury in this test portion is reduced, makes the oxidized gas of said determination object test portion or above-mentioned test portion gas cyaniding compare mensuration by oxidation catalyst.
In addition, the present invention is the mercury determinator in the above-mentioned coal combustion emission gases, it is characterized in that it possesses and has: import the road from the above-mentioned test portion of removing the device heating and importing above-mentioned test portion, be filled with the reactive low of acidic materials and have the reducing catalyst portion of catalyzer of the dead matter of reducing power for mercury, be provided with the reduced gas stream of above-mentioned reducing catalyst portion, filled the oxidation catalyst portion of oxidation catalyst, be provided with the oxidized stream of above-mentioned oxidation catalyst portion, the ultraviolet light-absorbing type analysis meter of the mercury concentration in above-mentioned reduced gas of comparative measurements and the oxidized gas.
When measuring the mercury in the coal combustion emission gases, be present in SeO in the emission gases in processing
2The time, as mentioned above, the problem that exists several needs to solve.That is, in the coal combustion emission gases, mercury is with Hg
2+Or Hg
0State exist, simultaneously, coexistence has for ultraviolet absorptiometric analysis meter and causes interference effect, causes the SO of error at measurment
2, NO
2And moisture etc.Among the present invention, preparing has the mercury selective reduction in the test portion, full mercury is transformed to Hg
0Reduced gas, and with the mercury selective oxidation in the test portion, full mercury is transformed to Hg
2+Oxidized gas, by
(1) under the ultraviolet extinction ware (test portion ware) of ultraviolet light-absorbing type analysis meter is single situation, alternately imports reduced gas and oxidized gas to the test portion ware, relatively both extinction amounts;
(2) under the situation of above-mentioned test portion unit for plural number (being generally 2), import reduced gas and oxidized gas simultaneously to each test portion ware, relatively both extinction amounts;
Can under situation about not being subjected to not, measure with the influence of other coexistence compositions of oxidation processes and reduction processing variation.
Thereby, for 1 test portion, carry out oxidation and reduction by serial or parallel connection, follow both to handle the difference of mercury state in the test portion that difference produces by mensuration, can guarantee that the high selectivity when mercury in the coal exhaust is measured is measured precision.
Concrete, by using the catalyzer with reactive low, the inorganic of acidic materials, can get rid of the SO that contains in a large number in the coal combustion emission gases with reducing power
2, NO
2The intoxication of the catalyzer that produces Deng acidic materials.In addition, import ultraviolet light-absorbing type analysis meter, can guarantee the analytic function identical, can carry out the mensuration of the higher mercury concentration of precision with atomic absorption spectrography (AAS) by the test portion that will carry out this kind processing.
Here, " with the reactive low of acidic materials and have the catalyzer of the inorganic of reducing power for mercury " refers to, and the compound of the inanimate matter of the catalyzer of hereinafter described zeolite system or alkali-metal sulphite etc. has mercuric chloride (HgCl
2) wait the mercury (Hg of divalent
2+) compound be reduced to metal (Hg
0) function the time, with the SO that contains in a large number in the coal combustion emission gases
2, NO
2Deng the lower catalyzer of the reactivity of acidic materials.
The effect of invention
As mentioned above, according to the present invention, can provide:, can remove the method and apparatus of element S e simple to operate, steadily in the long term in order to prevent the middle generting element Se such as mercury mensuration in the coal combustion emission gases, wherein, element S e is by the SeO that is present in the emission gases
2And produce, can counteract in the mercury mensuration in the coal combustion emission gases etc., this is former to be very difficult.In addition, but can provide used this remove method and remove device, mercury assay method and determinator in the coal combustion emission gases of the influence of the composition that do not coexisted, high precision and long-time stability high METHOD FOR CONTINUOUS DETERMINATION.
Particularly, by the combination of reducing catalyst portion and oxidation catalyst portion, comparative measurements all gases, high-precision mensuration is carried out in the influence of the composition that can not coexisted further.
Description of drawings
The selenium oxide that [Fig. 1] demonstration the present invention relates to is removed the key diagram of the 1st structure example of device.
[Fig. 2] summary shows that it is the key diagram of an employed cooling tube that the test portion that the present invention relates to is handled.
[Fig. 3] summary shows that it is the key diagram of employed secondary cooling tube that the test portion that the present invention relates to is handled.
[Fig. 4] summary shows that it is the key diagram of employed cooling processing portion that the test portion that the present invention relates to is handled.
[Fig. 5] shows that the selenium oxide that the present invention relates to removes the key diagram of application examples of the 1st structure example of device.
The selenium oxide that [Fig. 6] demonstration the present invention relates to is removed the key diagram of the 2nd structure example of device.
The selenium oxide that the demonstration of [Fig. 7] summary the present invention relates to is removed the key diagram of test unit.
The selenium oxide that [Fig. 8] demonstration the present invention relates to is removed the key diagram of the 3rd structure example of device.
The selenium oxide that [Fig. 9] demonstration the present invention relates to is removed the key diagram of the 3rd structure example of device.
[Figure 10] shows the key diagram of 1 structure example of the mercury determinator that the present invention relates to.
The key diagram of the structure example of other of the mercury determinator that [Figure 11] demonstration the present invention relates to.
[Figure 12] summary shows the key diagram of the analytical equipment structure that conventional art relates to.
[Figure 13] summary shows the key diagram of the analytical equipment structure that conventional art relates to.
The explanation of symbol
1 heating duct
The 1a test portion is discharged the road
2 cooling tubes
3 secondary cooling tubes
3a electronics cooling tube
4 regenerators
The 5a condensated water recovering pump
The 5b bosh
5c chilled water charge pump
The 5d flowmeter
7 scrubbing towers
10 ultraviolet light-absorbing type analysis meters
11 test portions inlet
12 dust filter units
13 reducing catalyst portions
14 filtrators
15 suction pumps
Embodiment
Below at example of the present invention, describe with reference to accompanying drawing.
＜originally remove the structure example of device 1 〉
The feature that the selenium oxide that the present invention relates to is removed one of device (hereinafter referred to as " originally removing device ") is that possessing has:
(1) the heat heating of test portion imports the road,
(2) have this heating test portion stream and cooling water flow form convection current stream, will heat test portion and chilled water mixing a cooling end afterwards to cool off,
(3) have the spiral fashion stream, simultaneously of the above-mentioned mixed gas of cooling, have the secondary cooling end in the space of carrying out gas-liquid separation in the terminal of this spiral fashion stream,
(4) import regenerator from the condensate water of this secondary cooling end,
(5) chilled water that connects this regenerator and a cooling end is supplied with the road.
The concrete structure of originally removing device 1 is in Fig. 1 illustration (the 1st structure example).Comprise: heating duct 1 (be equivalent to heating import road), a cooling tube 2 (being equivalent to cooling end one time), secondary cooling tube 3 and the electronic cooler 3a (being equivalent to the secondary cooling end) of its cooling, the regenerator 4 that is filled with anion exchange resins, condensated water recovering pump 5a, bosh 5b, chilled water charge pump 5c and flowmeter 5d (form chilled water and supply with the road).
Include moisture and SeO
2Deng test portion by heating duct 1, heat while condensation do not occur and to be transferred, import a cooling tube 2 and then mix with chilled water.At this, in the time of quench cooled, Yi Bian dissolve SeO in the test portion
2, then import secondary cooling tube 3.At this, when further being cooled, gas-liquid is separated, discharges road 1a from secondary cooling tube 3 tops by test portion, is discharged from as the test portion of the drying that disposes.
On the other hand, store chilled water in bosh 5b by chilled water charge pump 5c, by being supplied to cooling tube 2 behind the flowmeter 5d one time.When cooling off test portion (chilled water is heated) here, on one side dissolving remove SeO in the test portion
2, then import secondary cooling tube 3 with test portion.At this, when cooling off by electronic cooler 3a, gas-liquid is separated, and 5b is absorbed by condensated water recovering pump, by being recovered to bosh 5b behind the regenerator 4 that is filled with anion exchange resins.In the regenerator 4, be dissolved in the SeO of chilled water
2Be removed with other water-soluble substanceses, be regenerated as the clean chilled water of cleaning.
Here, at SeO
2Be dissolved in condensate water and describe, the effect of each inscape is described with mechanism that the mercury alloy of mercury generates.
[SeO
2Be dissolved in condensate water and with the mercury alloy formation mechanism of mercury]
(a) as shown in the formula 1, SeO
2For water-soluble, become H
2SeO
3The result of checking shows that this rapidly response carries out.
SeO
2+ H
2O → H
2SeO
3(formula 1)
(b) as shown in the formula 2 or 2 ', the H of generation
2SeO
3SO by a large amount of coexistences in the emission gases
2Be reduced, become metal Se.The checking result shows that this reaction is carried out comparatively gently, SeO
2Be not after being dissolved in water, to generate at once.Experiment showed, to H
2SeO
3Import certain density SO in the aqueous solution
2During gas, become yellow～orange, generate dense orange precipitation (elemental selenium Se) gradually.Being created under the high-temperature dew point environment of Se generates rapidly, is attached to tube wall etc. in case separate out, and then is difficult to clean by water filling.
H
2SeO
3+ SO
2→ Se+H
2SO
4(formula 2)
H
2SeO
3+ 2SO
2+ H
2O → Se+2H
2SO
4(formula 2 ')
(c) the metal Se that is produced is water insoluble, as shown in the formula 3, becomes the red powder shape at the pipe arrangement inwall, easily generates mercury alloy with the mercury of separating out.
Hg+Se → HgSe ... (formula 3)
[originally removing the structure of device]
(1) heating imports road (heating duct 1)
Test portion is heated to 100～200 ℃.Can prevent the condensate moisture in the test portion, the selenous acid (H that the reaction of supression following formula 1 causes
2SeO
3) generation.In addition, under the situation that is suppressed at solution shape water (comprising the water droplet and the spittle) existence, the SO in the test portion
2Or NO
2The generation of the elemental selenium that causes with the reaction of following formula 2 prevents the reaction of following formula 3, can suppress mercury in the test portion and the reaction of Se.
(2) cooling ends (cooling tube 2)
The test portion that is heated to 100～200 ℃ is passed through a cooling tube 2, in environment temperature, mix with chilled water in quench cooled.By following formula 1, the SeO in making test portion
2When being dissolved in chilled water,, clean with chilled water for the residual selenous acid that has following formula 1 to be produced on streams such as cooling tube not.At this, cooling tube 2 is so long as possess the corrosion stability that above-mentioned functions is arranged, then its structure and material and indefinite, but all as shown in Figure 2 structures are comparatively desirable.Being T word tube shape, is the top with chilled water inlet 2a, and inside is inserted with for example 3 φ/tubule (test portion conduit) 2b such as 2 φ fluoride resin pipe arrangements.The chilled water that is directed into a cooling tube 2 flows into test portion conduit 2b from chilled water inlet 2a by the inclination cut part 2c that is arranged on heating duct 1 exit portion, promotes the cooling of test portion gas and the SeO in the test portion gas
2Be dissolved in chilled water.By this structure, can keep quench cooled steadily in the long term.Test portion conduit 2b links to each other with secondary cooling tube 3, and the chilled water that contains selenous acid that dissolving generates and the mixed gas of test portion are discharged from from test portion conduit 2b, are supplied to secondary cooling tube 3.
(3) secondary cooling end (secondary cooling tube 3 and with the electronics cooling end 3a of its cooling)
Secondary cooling tube 3 is so long as can be in the cooling of the gas-liquid mixture fluid that effectively carries out chilled water and condensate water (hereinafter referred to as " chilled water etc. ") and test portion, can improve the rate of outflow, help to clean, to have corrosion stability in the cooling tube, then its structure and material are also unrestricted, but structure shown in Figure 3 is comparatively desirable.The secondary cooling tube 3 that is arranged in electronic cooler 3a or the water-cooled chiller has been to use 2 of glass tube to weigh tubular constructions, constitute by spiral fashion stream 3d between outer tube 3b that is arranged at the heat exchange department that is connected electronic cooler 3a and the interior pipe 3c and the space 3f that is arranged at its terminal 3e, accelerate the outflow of the cooling of test portion and chilled water etc.The test portion that has passed through stream 3d carries out the separation of chilled water etc. at the space of bottom 3f, and the internal flow path 3g by interior pipe 3c is discharged from.Therebetween, the test portion that is cooled carries out heat interchange with test portion by stream 3d.Though heat-shift can be not too many, the heat interchange by the higher test portion of the temperature of the low temperature test portion of discharging and importing is reheated, and can prevent dewfall.By using 3 pairs of test portions of this secondary cooling tube to handle, can prevent to generate the element S e that counteracts.On the other hand, chilled waters etc. re-use from being recycled space 3f discharges stream 3h by condensate water after, the test portion quench cooled of being undertaken by cooling tube 2 and add chilled water to test portion, can increase condensate flow, handle under the often mobile state of system at test portion, the condensate flow that produces is divided discharge outside the system.The condensate water that does not carry out cycling and reutilization, makes nature fall is detained with kettle, also might generting element Se in the test portion stream that be not only the condensate water stream, links to each other therewith.
(3 ') cooling processing portion 6
As shown in Figure 4, the admission port 6i of chilled water is set in the upstream of spiral helicine stream 6d, the combination of substituting disposable cooling tube 2 and secondary cooling tube 3 can use the structure of supplying with chilled water from here (hereinafter referred to as " cooling processing portion 6 ".)。Have by use: the test portion supply port 6j in 6i downstream, admission port, be arranged on the terminal 6e of stream 6d the space 6f that carries out gas-liquid separation, discharge stream 6h and the discharge stream 6g of the gas that disposes, the cooling processing portion 6 of structure of cooling off the electronic cooler 6a of each stream and space 6f by the condensate water of 6f shunting, can when obtaining the same effect, realize the densification of cooling processing portion 6.In addition, in the test portion eudiometry and in the correcting gas inspection, similarly, also can carry out the moisture interpolation by injecting chilled water, high-precision correction is carried out in the saturated dilution rate of revisal moisture and moisture interference influence fully.
(4) regenerator 4
Discharge chilled water that stream 6h flows down etc. from the condensate water of secondary cooling tube 3, be reproduced by regenerator 4, as the chilled water cycling and reutilization.In the regenerator 4, be filled with the reagent of removing the selenous acid that causes the obstruction in chilled water etc.Concrete, can use the adsorbent of anion exchange resins or selenous acid, ferriferous oxide (for example iron protoxide (FeO) and shrink ferric hydroxide (FeOOH) etc.) etc. for example, but the anion exchange resins that can carry out reagent autosynthesis ideal comparatively.In this device, fill the anion exchange resins of the 250g that has an appointment, often have the chilled water etc. of 1～10ml/min to pass through.Show that for the exchange of chilled water and the checking result that replenishes the frequency of maintenance that waits past must replenish in per 1 month, but pass through use anion exchange resins, extended to 3～6 months.In addition, regenerator 4 the downstream that can be positioned at secondary cooling end 3 unlike Fig. 1 is set, also can be arranged at front or the back of chilled water charge pump 5c.
(5) chilled water is supplied with road (condensated water recovering pump 5a, bosh 5b, chilled water charge pump 5c and flowmeter 5d)
Discharge chilled water that stream 6h flows down etc. from the condensate water of secondary cooling tube 3, by regenerator 4, condensated water recovering pump 5a, bosh 5b, chilled water charge pump 5c and flowmeter 5d, as chilled water often to import a cooling tube 2, cycling and reutilization about 1～10ml/min.Because condensated water recovering pump 5a and chilled water charge pump 5c will reclaim the almost certain amount of supply, the general piping pump that uses, but owing to can cause that the elastic force of pipe (tube) descends and sulfur content descends, therefore as shown in Figure 1, outlet at chilled water charge pump 5c is provided with flowmeter 5d, and it is comparatively desirable to carry out traffic monitor and flow revisal regularly.In addition, the chilled water of cycling and reutilization stops and producing water droplet, can generate mercury alloy, and the flowmeter 5d that therefore recirculated cooling water is set is comparatively desirable.In addition, method as the traffic monitor of chilled water of cycling and reutilization etc., can use liquid level detectors (not shown) such as float switch, the increase of the water yield in the certain hour of bosh 5b is detected, also can carry out the revisal of chilled water supply flow rate from detected flow.
[originally removing the application examples of device]
For originally removing device,, can replace or remove the said structure key element or increase other key elements according to the test portion condition.In addition, in order more effectively to utilize cooling processing portion 6, also can be structure as shown in Figure 5.Promptly, the chilled water that stores at bosh 5b is shunted by chilled water charge pump 5c and flowmeter 5d, when supplying to cooling tube 2 and cooling processing portion 6, by with a cooling tube 2 and cooling processing portion 6 arranged in series, carry out 2 phase process of chilled water, can further effectively prevent generting element Se in the stream.
[originally removing the embodiment of device]
(1) experiment condition
From the upstream of the heating duct of originally removing device 1 shown in Figure 1, about 1.1L/min imports the SeO that contains 18ppm with flow
2Gas.
(2) experimental result
(ICP, hole field make manufacturing, form: ULTIMA2) measure the chilled water that bosh 5b reclaims, the Se concentration that obtains dissolving is 5ppb with induction coupling high frequency plasma method.From the amount 300g of the chilled water of cyclic system, calculate the SeO of dissolving
2Total amount, calculating and removing efficient is 95%.
＜originally remove other structure examples of device 〉
Another the feature of originally removing device is to have
(1) the heat heating of test portion imports the road,
(2) be filled with the scrubbing tower of barium compound or ferriferous oxide or their potpourri,
(3) this scrubbing tower is maintained the heating arrangement of uniform temperature,
Carry out the selectivity of selenium oxide and remove processing.
The concrete alternative structure of originally removing device is (the 2nd structure example) as shown in Figure 6.Comprise: heating duct 1 (be equivalent to heating import road), be used to remove SeO by what heating arrangement (not shown) heated
2Scrubbing tower 7, secondary cooling tube 3 and with electronic cooler 3a, the bosh 5b of its cooling.
Include moisture and SeO
2Deng test portion by heating duct 1, heat and be transferred for condensation not occurring on one side, importing is heated to the scrubbing tower 7 of uniform temperature, removes the SeO in the test portion
2After, import secondary cooling tube 3.At this, the condensate water that produces of being cooled is discharged road 1a by gas-liquid separation from secondary cooling tube 3 tops by test portion, is discharged from as the test portion of the drying that disposes.On the other hand, stored at bosh 5b by the condensate water of gas-liquid separation in the secondary cooling tube 3.
[SeO
2Selecting of remover]
(1) for the checking of various metallic compounds
(1-1) experiment condition
Use test unit shown in Figure 7, the various metallic compounds that can be used as scrubbing tower 7 uses are filled in the scrubbing tower unit 7a, the order test was tested with about 1.1L/min circulation with gas in 3 hours.Test with gas is: will contain SO
2The gas of 500ppm imports and is set at 200 ℃ SeO
2Gasification installation 7b, SeO
2Concentration is the gas of 18ppm.Same, make in advance and determined mercuric chloride (HgCl
2) calibrating gas (the 50 μ g/m of generation concentration
3).Making the heating-up temperature of scrubbing tower 7 is 150～250 ℃, makes the gas that has passed through scrubbing tower pass through SeO
2Trapping solution 7c is for SeO
2The amount of not removing test.The detection of the amount of not removing, the rate of removing judge it is by the SeO in the trapping solution
3The ion concentration assay value is measured, and analyzes lysed Se concentration.On the other hand, include HgCl
2Gas after secondary cooling end 3 dehumidifies, measure by ultraviolet analysis meter 10, test for influences such as having or not scrubbing tower absorption loss.Remove SeO in the trapping solution
3Removing beyond the rate of ion concentration assay value, the rate of removing are judged the degree of also having considered to have or not in the scrubbing tower outlet pipe arrangement yellow～black tea look precipitate.
(1-2) experimental result
Experimental result is as shown in table 1.In the various metallic compounds, for barium compound (barium carbonate (BaCO
3)) and iron (III) oxide (shrink ferric hydroxide), under about 200 ℃ of temperature range, be met SeO
2The good result who removes rate (more than 99%) and do not have Hg (0) adsorption conditions.Mark zero expression effect excellence, the work of failing to remove mark.
[table 1]
(2) characteristic of barium compound
The result of above-mentioned checking shows, barium carbonate (BaCO
3) or barium sulfite (BaSO
3) wait barium compound to pass through the reaction shown in the following formula 6,7, with SeO
2In the time of selective reaction, can set the condition (temperature conditions: 150-250 ℃) that is subjected to react or adsorb the influence that causes hardly with mercury.
SeO
2+ BaCO
3→ BaSeO
3+ CO
2(formula 6)
SeO
2+ BaSO
3→ BaSeO
3+ SO
2(formula 7)
As above shown in the table 1, can guarantee 200 ℃ of rates of removing more than 99% down.In addition, in fact, there is coexistence gas moisture, reacts, have section H in order to promote
2SeO
3Form and help reaction.
(3) characteristic of ferriferous oxide
Iron protoxide (FeO) and shrink ferric hydroxide ferriferous oxides such as (FeOOH) are by the reaction shown in following formula 5 or the following formula 8-10, with SeO
2Selective reaction generates Fe
2(SeO
3)
3In addition, under temperature conditions 150-250 ℃, be subjected to the influence that causes with mercury reaction or absorption hardly.As above shown in the table 1, can guarantee 200 ℃ of rates of removing more than 99% down.
XSeO
2+ yFeO → Fe
xSe
y+ (x+y/2) O
2(formula 5)
3SeO
2+ 2FeO+1/2O
2→ Fe
2(SeO
3)
3(formula 8)
3SeO
2+ 2FeOOH → Fe
2(SeO
3)
3(formula 9)
3SeO
2+ Fe
2O
3→ Fe
2(SeO
3)
3(formula 10)
(4) characteristic of potpourri
As the reagent of selenium oxide remover, illustration barium compound and ferriferous oxide, but but by their mixing use life-saving.The reason that life-span descends is the selenite (MSeO that reaction is generated
3Or M
2(SeO
3)
3Deng, M refers to Ba or Fe here.) cause, but use the reagent of removing scrubbing tower separately, and can generate the independent salt of selenite, generating independent salt on the fine crystal of reagent powder is the reason that causes decrease in efficiency.Compare to independent salt, the xenogenesis reagent forms potpourri can make it be difficult to form.
(5) filling agent of scrubbing tower
Mentioned reagent is powder or micro-crystallization reagent, and as the filling agent of scrubbing tower, the granular detergent tower that barium carbonate, ferriferous oxide etc. form is comparatively desirable.Prilling process is to use bond liquid to carry out granulation or granulating for inorganic porous plastid particle.Great river chemical industry Co., Ltd.) or activated alumina concrete, as inorganic porous plastid particle, (trade name:, bond uses water glass or lithium metasilicate etc. to use パ ミ ス タ one.This filling agent is arranged at the leading portion of Hg reducing catalyst, can not be subjected to moisture and SO in the exhaust
2Deng influence and selectivity is removed SeO
2, can stablize and carry out accurately full mercury mensuration.
＜originally remove the 3rd structure example of device 〉
The feature of originally removing the 3rd structure example of device is: refrigeratory and recoler combination or cooling processing portion and scrubbing tower set with serial or parallel connection.Although wet process can still can be kept and removes efficient through long-time use, on the contrary, compare with dry-cure that to remove efficient lower.In addition, according to the coexistence composition in the test portion, the test portion disposal route can limit to some extent.Although dry-cure can guarantee high selectivity and remove efficient,, can be consumed because of reaction as the barium compound or the ferriferous oxide of scrubbing tower, therefore have term of life.The present invention is by two kinds of method serial or parallel connections are made up, in the hope of use that they are complemented one another.
(1) situation of arranged in series
As shown in Figure 8, a refrigeratory 2 sets to connect with recoler 3 and scrubbing tower 7.Remaining micro-SeO in the test portion of handling by refrigeratory 2 and recoler 3
2, can be reduced to the ultramicron rank by scrubbing tower 7.In addition, because wet process is suitable for long-term use, therefore, can constitute the test portion disposal system that to bear long-term use by a refrigeratory 2 is arranged on the upstream with recoler 3.
(2) situation of configuration in parallel
As shown in Figure 9, a refrigeratory 2 sets with in parallel with recoler 3 and scrubbing tower 7.For example, in the coal combustion boiler etc., owing to when boiler is brought into use, contain a large amount of mercury or SeO in the test portion
2Deng, when running well, they can become trace.Under the corresponding situation, by wet process configuration in parallel, carry out wet process, carry out dry-cure the latter at the former with dry-cure, can replenish both load, lighten the load.
[originally removing the embodiment of device]
(1) experiment condition
The upstream of the heating duct of originally removing device 1 that sets to connect from a refrigeratory 2 shown in Figure 8 and recoler 3 and scrubbing tower 7, about 1.1L/min imports the SeO that contains 18ppm with flow
2Gas.
(2) experimental result
(ICP, hole field make manufacturing, form: ULTIMA2) measure the chilled water that bosh 5b reclaims, the Se concentration that obtains dissolving is 5ppb with induction coupling high frequency plasma method.From the amount 300g of the chilled water of cyclic system, calculate the SeO of dissolving
2Total amount, calculating and removing efficient is 95%.
＜used the structure example of the mercury determinator in the coal combustion emission gases of originally removing device 〉
The feature of having used the structure example (hereinafter referred to as " this determinator ") of the mercury determinator in the coal combustion emission gases of originally removing device is to be the determination object test portion with the coal combustion emission gases, possesses the test portion collection portion of gathering above-mentioned test portion is arranged, imports road, above-mentioned device, the mercury analysis meter removed from this test portion collection portion heating and the test portion that imports above-mentioned test portion.For the SeO that is present in the coal combustion emission gases
2, coexisting in this emission gases has than juicy, SO
2And NO
2Deng condition under, easily make mercury and mercury alloy, be to cause to measure one of great reason that precision significantly descends, apparatus of the present invention can be got rid of this influence by using above-mentioned to remove device, the past method of can guaranteeing mensuration precision that is beyond one's reach.
Figure 9 shows that 1 structure of this determinator.In this structure, be applicable to that determination object is as divalent mercury (Hg
2+) and element mercury (Hg
0) wait the full mercury (Hg of such a plurality of compositions that comprise identity element, conversion mutually
2++ Hg
0).That is, at first with the Hg in the test portion gas
2+Full dose is transformed to mensuration determination object---Hg
0After, use above-mentioned the gas of removing after device analysis is handled, can get rid of SeO like this
2Wait the influence of other coexistence compositions.Below, as concrete embodiment, lift an example explanation: use wet process as originally removing device, will having used the mercury determinator in the coal combustion emission gases of ultraviolet light-absorbing type analysis meter 10 to be used for the present invention as determinator.
By being arranged at the suction pump 15 in ultraviolet light-absorbing type analysis meter 10 downstreams, test portion is gathered from 11 (the being equivalent to the test portion collecting part) attraction of test portion inlet.After the test portion of gathering cleaned by dust filter unit 12, the full mercury in the test portion is transformed to Hg by reducing catalyst portion 13
0, import ultraviolet light-absorbing type analysis meter 10 by heating duct 1, cooling end 2, secondary cooling end 3 and filtrator 14 backs.At this moment, the material as contact gas can use outside inexpensive glass, quartz, the pottery etc., can use Ti, oxidation processes SUS as metal.
Reducing catalyst portion 13 is unit that inside is filled with reducing catalyst, reducing catalyst by heating arrangement (not shown) maintain wherein temperature range 250-500 ℃ comparatively desirable.That is, general, the mercury in the coal combustion emission gases is with HgO, HgCl
2Or Hg
0State exist, be with Hg
2+Be reduced to Hg
0, pyrolysis is must be obligato, by making reduction temperature more than 250 ℃, can prevent owing to contained SeO in the exhaust
2Deng the reaction of metal oxide and produce mercury and mercury alloy.On the other hand, by making reduction temperature, can prevent in advance that the corrosion of test portion stream or reactant from causing problems such as obturation below 500 ℃.
The reducing catalyst that is filled in reducing catalyst portion 3 comparatively it is desirable to: with the catalyzer of reactive low, the inorganic with reducing power of acidic materials.Among the present invention,, require to have mercury (Hg with divalents such as mercuric chloride for reducing catalyst
2+) compound be reduced to metal (Hg
0) function the time, also require for other the coexistence composition unaffected and for other the coexistence compositions do not impact, promptly the mercury for divalent has selectivity.As the object lesson of reducing catalyst, can use the compound of such inanimate matter such as the catalyzer of zeolite system or alkali-metal sulphite.For reducing action, though also can use carbonate or hydroxy salt etc., by the SO that contains in a large number in the coal combustion emission gases
2, NO
2Deng the coexistence of acidic materials, from functional this kind catalyzer that is defined in.The shape of reducing catalyst is not particularly limited, but be easy to be filled to reducing catalyst portion 3 or be easy to exchange, spheroidite that the pressure loss is less or cellular etc. comparatively desirable.At this moment, not only can use the moulding of catalyzer own for this kind shape, also can use with this kind and be shaped as appendix body, appendix in the catalyzer on surface.
Though ultraviolet ray light-absorbing type analysis meter 10 is not shown, is formed with the optical system that ultraviolet light source portion, test portion ware portion, ultraviolet detector and optical filter constitute, and measures the Hg in the test portion that is imported into test portion ware portion by ultraviolet detector
0Ultraviolet region in absorbing amount, can measure the Hg in the test portion
0Concentration.
Other structure example of＜this determinator 〉
The feature of this determinator is that it possesses and has: import the road from the above-mentioned test portion of removing the device heating and importing above-mentioned test portion, be filled with the reactive low of acidic materials and have the reducing catalyst portion of catalyzer of the dead matter of reducing power for mercury, be provided with the reduced gas stream of above-mentioned reducing catalyst portion, filled the oxidation catalyst portion of oxidation catalyst, be provided with the oxidized gas stream of above-mentioned oxidation catalyst portion, the ultraviolet light-absorbing type analysis meter of the mercury concentration in above-mentioned reduced gas of comparative measurements and the oxidized gas.This determinator uses above-mentioned to remove device, is present in SeO in the emission gases in processing
2The time, reduce the SO that coexists
2, NO
2And the error at measurment of the disturbing effect that causes of composition such as moisture etc., can guarantee that the high selectivity that the mercury in the coal emission gases is measured measures precision.
Figure 11 is other example of structure of this determinator.This determinator at: use scrubbing tower 7 (dry-cure) as originally removing device, having used residual quantity formula analysis meter to describe as the structure of the full mercury determinator in the test portion of ultraviolet light-absorbing type analysis meter 10.Prepare in the selective reduction test portion mercury, make contained full mercury be transformed to Hg
0Reduced gas, and the selective oxidation test portion, make full mercury be transformed to Hg
2+Oxidized gas, by
(a) under the ultraviolet extinction ware (test portion ware) of ultraviolet light-absorbing type analysis meter is single situation, alternately import reduced gas and oxidized gas to the test portion ware, relatively both extinction amounts
(b) under the situation of above-mentioned test portion ware for plural number (being generally 2), import reduced gas and oxidized gas simultaneously to each test portion ware, relatively both extinction amounts can not be subjected to not measure with other influences that coexist compositions of oxidation processes and reduction processing variation.Therefore,, carry out oxidation and reduction, mensuration because the difference of mercury state in the test portion that both processing difference produces can not be subjected to the influence of other coexistence gas componants, guarantee to measure precision by serial or parallel connection for 1 test portion.
By being arranged at the suction pump 15 in ultraviolet light-absorbing type analysis meter 10 downstreams, test portion is attracted to gather from test portion inlet 11.After the test portion of gathering cleaned by dust filter unit 12, remove SeO in the test portion with scrubbing tower 7
2, pass through reducing catalyst portion 13 again with the mercury selective reduction in the test portion, be made into contained full mercury and be transformed to Hg
0Reduced gas.Then, be divided into two via secondary cooling end 3 (gas-liquid separator), a side (stream a) in, remove Hg in the test portion by treater 16
0, or test portion in mercury by optionally oxidation, be made into contained full mercury and be transformed to Hg
2+Oxidized gas, import ultraviolet light-absorbing type analysis meter 10 via valve 17.Among the opposing party (stream b), do not do any processing, import ultraviolet light-absorbing type analysis meter 10 via valve 17.At this moment, the material as contact gas can use outside inexpensive glass, quartz, the pottery etc., can use Ti, oxidation processes SUS as metal.
During common mensuration, by valve 17, stream a and stream b are periodically switched, by both difference, Hg
2+Measured by ultraviolet light-absorbing type analysis meter 10.Timing, zero point, gas and span gas were imported into from correcting gas inlet 18, were imported into ultraviolet light-absorbing type analysis meter 10 via stream d.What span gas used is the gas that contains the finite concentration mercury that produces in the generator (not shown) that imports gas at zero point.The switching of valve 17 is generally carried out with about 0.5 second-30 seconds cycle.
The temperature of the test portion stream from test portion collection portion 11 to ultraviolet light-absorbing type analysis meter 10 is set as follows shown in the table 2, contains dust filter unit 12, prevents to produce condensing water or generates SeO
2With the mercury alloy of mercury, keep scrubbing tower 7 proper temperature 150-250 ℃.
[table 2]
| Beyond the pre-treatment portion that mercury is measured | Design temperature (℃) |
| Flue gas | 200-350℃ |
| Sound-pipe | 190-200℃ |
| The F1 element | 190-200℃ |
| SeO 2Scrubbing tower | 150-250℃ |
| The Hg reducing catalyst | 250-500℃ |
| Gas-liquid separation portion | 5-30℃ |
| Determination unit | 55 ℃ of calibration cells |
As treater 16, for example, by using adsorbent such as activated charcoal, can selective adsorption remove the Hg in the test portion
0In addition, for example, use Pt-silicon system or Pd-alumina series or V
2O
5Deng catalyzer, by with the Hg in the test portion
0Being oxidized to ultraviolet light-absorbing type analysis meter 10 can't detected Hg
2+, can selectivity remove Hg
0At this moment, use under the situation of oxidation catalyst as treater 16, operating temperature can be set at the middle temperature range (for example 300-400 ℃) identical, both can be accommodated in the same unit, realize the unification of temperature control system, the densification of device with reducing catalyst portion 3.
The certain density Hg gas that is used to proofread and correct or checks can't be prepared as gases at high pressure, must use generator.For example, the method on the top layer by making the Hg of gas at zero point by maintaining uniform temperature perhaps will be infiltrated pipe and be immersed the Hg that Hg liquid bath, order soak into and sneak into gas at zero point, obtain certain density Hg gas with this.In addition, by making it, can obtain the Hg gas of low concentration with gas dilution at zero point.For the supply of calibrating gas, can supply with from the test portion portion of taking shown in Figure 11.
Ultraviolet ray light-absorbing type analysis meter 10 can use the structure identical with above-mentioned Figure 10, but also can use the formed structure of the optical system that is made of 2 test portion wares.In addition, under the test portion ware is single situation, as shown in figure 11, alternately import reduced gas and oxidized gas, relatively both extinction amounts to ultraviolet light-absorbing type analysis meter 10.On the other hand, contain under the situation of 2 test portion wares, import reduced gas and oxidized gas simultaneously, measure the residual quantity of both extinction amounts to each test portion ware.Owing to can detect both uptake poor, therefore can be used in the situation of the residual quantity of two test portions of direct mensuration.
By above structure, this determinator can obtain following technique effect.
(1) during the full mercury in the coal emission gases is measured, the less gas SeO that is subjected to coexisting
2Obstruction influence, realize high sensitivity measuration correct and steady in a long-term.
(2) can optionally remove obstruction composition---the SeO of mercury in measuring
2
(3), has the effect kept of performance of protection mercury catalyst by scrubbing tower being arranged on the leading portion of reducing catalyst portion.Reducing catalyst for back segment prevents SeO
2Obstruction influence.
(4) leading portion by scrubbing tower being arranged on reducing catalyst portion, operating temperature is maintained 150-250 ℃, can be used as the preparation heating performance function of reducing catalyst portion, can effectively utilize heat.
(5) because the operating temperature of scrubbing tower can maintain the identical degree of heating-up temperature of the pretreating device of measuring with mercury, structure that therefore can simplification device.
Other structure example of＜this determinator 〉
As other structure example of this determinator, with above-mentioned combination of removing device in can enumerate various structures.For example, in shown in Figure 8 and the combination of originally removing device, be equipped with test portion inlet 11, dust filter unit 12 and reducing catalyst portion 13 by provided upstream at heating duct 1, and then the back of scrubbing tower 7 is provided with filtrator 14, ultraviolet light-absorbing type analysis meter 10 and suction pump 15, expects connecting carrying out this determinator of wet process and dry-cure.Can guarantee higher SeO for a long time
2Remove efficient.
Industrial applicibility
Above, mainly the present invention is applicable to that mercury assay method in the Discharged form Coal Combustion gas and the situation of determinator are illustrated, but also can uses this mercury assay method and determinator for the similar test portion of composition and the research of various processing procedure in the process gas etc. In addition, for measuring SO2Or the test portion of the coexistence such as metal oxide is particularly useful.
Claims (12)
1. method of removing the selenium oxide in the test portion is characterized in that: with test portion under heating condition by being filled with the scrubbing tower of barium compound or ferriferous oxide or their potpourri, carry out the selectivity of selenium oxide and remove processing.
2. method of removing the selenium oxide in the test portion as claimed in claim 1 is characterized in that: also have
This test portion more than 100 ℃ is mixed, carries out the cooling processing of quench cooled to environmental gas temperature or 0～30 ℃ with chilled water,
When mixed gas is carried out the gas-liquid separation processing, the secondary cooling processing of cooling off again,
The condensate water that is reclaimed by this secondary cooling processing is carried out Regeneration Treatment,
The chilled water cycling and reutilization of using as an above-mentioned cooling processing.
3. method of removing the selenium oxide in the test portion as claimed in claim 2 is characterized in that: the selectivity of an above-mentioned cooling processing and the combination of secondary cooling processing, above-mentioned selenium oxide is removed processing and is carried out with serial or parallel connection.
4. the selenium oxide in the test portion is removed device, it is characterized in that: possess the importing road that has pair test portion to heat; Be filled with the scrubbing tower of barium compound or ferriferous oxide or their potpourri; This scrubbing tower is maintained the heating arrangement of uniform temperature, carry out the selectivity of selenium oxide and remove processing.
5. the selenium oxide in the test portion as claimed in claim 4 is removed device, it is characterized in that also possessing having:
Have the stream of this test portion stream and cooling water flow formation convection current more than 100 ℃ and this test portion and chilled water mixed carrying out the cooling end of quench cooled to environmental gas temperature or 0～30 ℃,
The secondary cooling end that has the space of carrying out gas-liquid separation when having the spiral fashion stream of cooling and mixing gas in the terminal of this spiral fashion stream,
Importing is from the regenerator of the condensate water of this secondary cooling end,
The chilled water that connects this regenerator and a cooling end is supplied with the road.
6. the selenium oxide in the test portion as claimed in claim 5 is removed device, it is characterized in that: the combination of an above-mentioned refrigeratory and recoler and above-mentioned scrubbing tower are with the serial or parallel connection setting.
7. the mercury assay method in the coal combustion emission gases is characterized in that:
This method has been used as any described method of removing the selenium oxide in the test portion in the claim 1～3,
With the coal combustion emission gases is the determination object test portion, after the above-mentioned test portion that uses above-mentioned method of removing the selenium oxide in the test portion that test portion collection portion is collected is handled, measures by the mercury analysis meter.
8. the mercury assay method in the coal combustion emission gases is characterized in that:
This method has been used as the selenium oxide in any described test portion in the claim 4～6 and has been removed device,
With the coal combustion emission gases is the determination object test portion, use above-mentioned remove above-mentioned test portion that device collects test portion collection portion and handle after, measure by the mercury analysis meter.
9. the mercury assay method in the coal combustion emission gases as claimed in claim 7, it is characterized in that: after using above-mentioned method of removing the selenium oxide in the test portion that above-mentioned test portion is handled, utilize ultraviolet light-absorbing type analysis meter, the mercury in this test portion has been had the reduced gas of catalyst reduction of inorganic of reducing power and the oxidized gas of said determination object test portion or the oxidized catalyst oxidation of above-mentioned test portion gas and compared mensuration.
10. the mercury assay method in the coal combustion emission gases as claimed in claim 8, it is characterized in that: use above-mentioned remove device above-mentioned test portion handled after, utilize ultraviolet light-absorbing type analysis meter, the mercury in this test portion has been had the reduced gas of catalyst reduction of inorganic of reducing power and the oxidized gas of said determination object test portion or the oxidized catalyst oxidation of above-mentioned test portion gas and compared mensuration.
11. the mercury determinator in the coal combustion emission gases is characterized in that:
This device has used as any described method of removing the selenium oxide in the test portion in the claim 1～3,
With the coal combustion emission gases is the determination object test portion, and possessing has: gather above-mentioned test portion test portion collection portion, from this test portion collection portion heating of above-mentioned test portion and the heating that imports are imported road, above-mentioned device and the mercury analysis meter removed.
12. the mercury determinator in the coal combustion emission gases is characterized in that:
This device has used as the selenium oxide in any described test portion in the claim 4～6 and has removed device,
With the coal combustion emission gases is the determination object test portion, and possessing has: gather above-mentioned test portion test portion collection portion, from this test portion collection portion heating of above-mentioned test portion and the heating that imports are imported road, above-mentioned device and the mercury analysis meter removed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-024456 | 2007-02-02 | ||
| JP2007024456A JP2008190950A (en) | 2007-02-02 | 2007-02-02 | Removing method and removing device for selenium oxide in sample, and measuring method and measuring device for mercury in coal combustion exhaust gas using them |
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| CN200810005096.5A Division CN101285743B (en) | 2007-02-02 | 2008-02-02 | Method and apparatus for removing selenium oxide, and method and apparatus for measuring mercury by using the same |
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| CN102175503B CN102175503B (en) | 2014-08-13 |
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| CN201110027788.1A Expired - Fee Related CN102175503B (en) | 2007-02-02 | 2008-02-02 | Method and apparatus for removing selenium oxide, and method and apparatus for measuring mercury by using the same |
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| CN108362828B (en) * | 2014-11-21 | 2020-02-18 | 中国环境科学研究院 | Mist liquid absorption device for collecting peroxides in atmosphere |
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Also Published As
| Publication number | Publication date |
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| CN101285743B (en) | 2013-06-12 |
| US20080188002A1 (en) | 2008-08-07 |
| JP2008190950A (en) | 2008-08-21 |
| CN102175503B (en) | 2014-08-13 |
| CN101285743A (en) | 2008-10-15 |
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